Int. J. Environ. Res., 6(3):663-668, Summer 2012
ISSN: 1735-6865
Nitrate and Chloride Concentrations in Groundwater beneath a Portion of the
Trinity Group Outcrop Zone, Texas
Hudak, P. F.
Department of Geography and Environmental Science Program, University of North Texas, 1155
Union Circle #305279, Denton, TX 76203-5017, USA
Received 22 Aug. 2011;
Revised 20 Nov. 2011;
Accepted 27 Nov. 2011
ABSTRACT: Using a geographic information system and statistics, we evaluated spatial distributions of
nitrate and chloride concentrations in groundwater in an area of north-central Texas with agricultural activity,
in addition to oil and natural gas exploration and production. Data were compiled from 40 water wells sampled
in 2007. Nitrate concentrations in three wells exceeded the maximum contaminant level (44 mg/L) for drinking
water. The highest nitrate concentration was 149 mg/L, and concentrations were generally higher in shallower
wells. Chloride concentrations exceeded the 250 mg/L secondary drinking water standard in two wells, with no
significant association between chloride concentration and well depth. Results of this study suggest localized
human impacts, especially for nitrate, and identify areas warranting future monitoring.
Key words: Nitrate,Chloride, Groundwater,Trinity Aquifer,Texas
INTRODUCTION
A highly soluble complex ion, nitrate is a common
contaminant in groundwater worldwide (Spalding and
Exner, 1993). Exposure to high nitrate concentrations in
drinking water over long time periods may cause colon
and rectum cancers, methemoglobinemia in infants, and
non-Hodgkin’s lymphoma (Ward et al., 1996;
Knobeloch et al., 2000; De Roos et al., 2003; Coetzee et
al., 2011). The standard, or maximum contaminant level
(MCL), for nitrate in drinking water is 44 mg/L (EPA
2009). Lots of studies are run regarding the groundwater
quality degradation through discharge of different
pollutants (Eneke et al., 2011; Belkhiri et al., 2011; Hudak,
2011;, Martinez-Paz and Perni, 2011; Romanelli et al.,
2011). There are many potential sources of nitrate in
groundwater, including fertilizers, septic tank effluent,
municipal sewage, animal feedlots, decaying
vegetation, and atmospheric deposition (Wilhelm et al.,
1996). In aerated soils, oxygen transforms nitrogen to
nitrate, which may percolate to groundwater. Annually,
U.S. farmers apply nearly 11 million metric tons of
nitrogen-bearing fertilizer to cropland and pastures
(Nolan et al., 1997); harvested crops remove only 40%
of that amount, leaving an excess in the environment
(Power, 1987). Animal manure contains another 6 million
metric tons of nitrogen, some of which is lost by
volatilization during storage and handling (Puckett,
1994). Other potential agricultural sources of nitrate
include organic nitrogen in plant detritus, bacterial
biomass, and soil constituents. For example, plowing
native vegetation releases nitrogen-bearing plant
detritus and aerates the soil, thus promoting nitrate
formation. Nonagricultural sources of nitrate include
septic systems, yard fertilizer, discharges containing
nitrogen-bearing effluent, and atmospheric deposition.
Upon reaching the saturated zone, nitrate tends to
stay in solution, rather than adsorb or precipitate onto
aquifer solids (Hem, 1985). Most public and private
water treatment systems do not remove nitrate from
well water. Determining sources of nitrate in
groundwater can be difficult; sometimes, associations
between nitrate concentrations and other parameters,
such as well depth and chloride concentrations, may
be useful for this purpose. Inverse associations
between nitrate concentration and well depth suggest
a shallow source, and direct associations between
nitrate and chloride concentrations may indicate a
common source. A soluble constituent of various
minerals, chloride resides in virtually all freshwater,
usually at low concentrations (Hem, 1985). Chloride
compounds may accumulate in cropland from
evaporated irrigation water and fertilizer. In areas with
oil and gas production, brine may also be a source of
*Corresponding author E-mail:[email protected]
663
Hudak, P. F.
chloride in surface soils or groundwater. Texas oilfield
brine averages 50,000 mg/L chloride (TWC, 1989).
Historically, oilfield brine produced in the U.S. was
discharged to surface excavations, natural depressions,
or gullies, and sprayed onto dirt roads. Presently, most
oilfield brine is injected into deep disposal wells;
however, both present and historical brine disposal
practices may contaminate groundwater (TDA, 1985).
High chloride concentrations may adversely impact
drinking water or irrigation water. The U.S. secondary
drinking water standard for chloride is 250 mg/L (EPA,
2009). In irrigation water, chloride concentrations
above 140 mg/L may damage sensitive crops; values
exceeding 360 mg/L may cause severe problems (Bower,
1978). Previous investigations suggested regions
within Texas susceptible to high nitrate concentrations
in groundwater (TWC, 1989; Hudak, 2000). This article
documents the occurrence and possible sources of
nitrate and chloride concentrations in groundwater
beneath agricultural land overlying a shallow aquifer
and deeper oil and gas reservoirs in north-central Texas,
USA (Fig. 1).
Group includes the Twin Mountains, Glen Rose, and
Paluxy Formations. The Twin Mountains Formation
consists of sand, shale, clay, and a basal gravel and
conglomerate (Peckham et al., 1963). A confining unit,
the Glen Rose Formation includes limestone, marl,
shale, and anhydrite. The Paluxy Formation consists
mainly of sand and shale. Thickness of water-bearing
sand zones within the Trinity Group ranges up to
approximately 15 m (Ulery and Brown, 1995). Farms
account for over 90% of the study area, with pasture
and cropland the predominant land cover (Table 1).
Forage (hay), pecans, wheat, and sorghum are major
crops grown in the study area. Farmers also raise
various livestock, including cattle, goats, quail, and
sheep. Patches of remnant oak forest, suited to welldrained soils, also occupy portions of the study area.
Currently, there are more than 5,000 oil and gas wells
(active, inactive, and injection) tapping Paleozoic
reservoirs beneath the study area (Table 1); mainly
these wells occupy the northwest half of the area. Well
depth, nitrate, and chloride concentrations were
compiled for 40 water wells in the Groundwater
Database of the Texas Water Development Board.
Water samples were collected in 2007. Sampled wells
served various uses, but primarily domestic (27 wells)
and public (7 wells) water supply. Other wells in the
dataset were used for irrigation (3 wells) and stock (2
wells), and one well was unused.
MATERIALS & METHODS
The study area comprises five counties—Brown,
Comanche, Eastland, Erath, and Mills—in a rural part
of north-central Texas (Fig. 1, Table 1). Throughout
this area, the Cretaceous Trinity Group provides
groundwater for several purposes. The aquifer is
unconfined in this area and vulnerable to
contamination from sources originating at or near the
land surface.
Depths of sampled wells ranged from 44 ft (13 m)
to 460 ft (140 m), with a median depth of 160 ft (49 m)
(Table 2, Fig. 2). Sampling and analysis followed
standard procedures described in TWDB (2003). After
measuring water depth, wells were pumped until
temperature, conductivity, and pH stabilized. Samples
were taken directly from each well, filtered, preserved,
and delivered to an analytical laboratory. Analyses
were completed using automated colorimetry or ion
chromatography.
Rainfall, irrigation, and influent surface water
recharge the Trinity Aquifer. On average, the study
area receives approximately 76 cm of precipitation per
year; approximately 2.5 cm recharges the aquifer (Baker,
1990). Average depth to groundwater in the study area
is about 15 m, and groundwater flows generally
southeastward. Water-bearing sand formations of the
Trinity Group outcrop within the study area and dip
underground to the east, where the aquifer becomes
confined (Baker, 1990). From bottom to top, the Trinity
MINITAB (Minitab, State College, Pennsylvania)
was used to compute descriptive statistics and rank
correlations among well depth and solute
concentrations. Rank correlations were computed
Table 1. Population and Land Use
Cou nty
Brown
Comanche
Ea stland
Er ath
Mills
Total Oil Well
Count s
1,237
121
1,418
28
1
T ot al G as
W ell Coun ts
701
244
1,177
515
3
Sources: Railroad Commission of Texas; U.S. Census Bureau
664
Population
38,088
13,559
18,167
36,184
4,994
Perc ent Land in
Far ms
93
97
88
90
99
Int. J. Environ. Res., 6(3):663-668, Summer 2012
Fig. 1. Five-county study area and sampled wells (x)
Fig. 2. Well depths; from smallest to largest, circles represent 44-100, 101-200, 201-300, and
301-460 ft; 1 ft = 0.31 m
665
Nitrate and Chloride Concentrations in Groundwater
because the data were non-normally distributed. Solute
concentration and well depth categories were mapped
with the ArcView (Environmental Systems Research
Institute, Redlands, California) geographic information
system.
A statistically significant, inverse association
between nitrate concentration and well depth (Table
3) is consistent with nitrate originating from
agricultural sources at or near the land surface. From a
planning perspective, an inverse association between
nitrate concentration and well depth suggests that
deeper wells may reduce the threat of pollution in
vulnerable parts of the study area. Agricultural
practices, especially fertilizer applications, probably
account for nitrate observations in the highest mapped
categories.
RESULTS & DISCUSSION
`Observed nitrate concentrations ranged from nondetected to 149 mg/L (Table 2, Fig. 3). Twenty-six of 40
samples had detectable nitrate levels; however, the
median concentration was only 2 mg/L (Table 2). Eleven
of 40 nitrate observations exceeded 10 mg/L, but only
three of those observations also exceeded the MCL of
44 mg/L.
Only two chloride observations surpassed the
secondary MCL of 250 mg/L. The highest chloride
Table 2. Summary of Solute Concentrations and Well Depths*
Paramete r
Nitrate ( mg/L)
Chloride ( mg/L)
Well de pth (ft)
M inimum
<0.44
2
44
Med ian
2
36
160
Maximum
149
595
460
*1 ft = 0.31 m
Fig. 3. Nitrate concentrations; from smallest to largest, circles represent <0.44, 0.44-10, 11-44,
and 45-149 mg/L
Table 3. Rank Correlations
Chlor ide
N itrate
D epth
C hlor ide
-0.159
-0.626*
0.265
*Statistically
significant at significance level of 0.01
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Int. J. Environ. Res., 6(3):663-668, Summer 2012
Fig. 4. Chloride concentrations; from smallest to largest, circles represent 2-20, 21-100, 101-250, and
251-595 mg/L
concentrations were in relatively shallow wells, less
than 100 ft (31 m) deep; these wells may have been
impacted by a contaminant source near the land
surface, for example, oil and gas activity or irrigation
return flow. However, over the entire study area, there
was no significant association between chloride
concentration and well depth. While natural
constituents of the Trinity Group likely exert a major
control on observed chloride concentrations,
anomalous concentrations (above 250 mg/L), and a
tendency for higher chloride concentrations in the
northwestern part of the study area (with much heavier
oil and gas activity), suggest possible human impacts.
Figs 3 and 4 show locations within the study area with
relatively high nitrate and chloride concentrations,
which have the potential to produce high
concentrations in present and future water wells.
Groundwater in these areas especially should be
periodically monitored to determine whether nitrate,
chloride, and other solute concentrations are suitable
for drinking, irrigation, or other intended uses. Both
concentration levels and water use dictate appropriate
filtration measures; for example, reverse osmosis could
remove nitrate, chloride, and other solutes from
drinking water, though this process is relatively
expensive. Less costly options may include treating
only drinking water, or consuming bottled water.
corn- and soybean-producing areas of the midwestern
United States. Moreover, Strebel et al. (1989) and Fried
(1991) reviewed nitrate pollution of groundwater in
Europe; highest nitrate concentrations, above 50 mg/
L, occurred in sandy soils beneath intensely managed
crops and grazed grassland. Furthermore, Zhang et al.
(1996) reported that more than 50% of sampled water
wells in a fertilized region of northern China had nitrate
levels above 50 mg/L. Very high concentrations, up to
300 mg/L, were found in groundwater beneath
vegetable-producing areas, small cities and towns, and
farmers’ yards. Chloride concentrations observed in
this study are low relative to those observed in some
areas with intensive agriculture and oil and gas
production. For example, Hudak (2003) compiled
samples from 198 water wells in the Edwards-Trinity
Plateau Aquifer of west-central Texas; 49 samples had
chloride concentrations above 250 mg/L, 22 samples
had greater than 500 mg/L chloride, and nine samples
exceeded 1,000 mg/L chloride.
CONCLUSION
In conclusion, out of 40 samples, only three nitrate
observations and two chloride observations exceeded
the respective drinking water standards. Shallower
wells within the study area tend to be more vulnerable
to nitrate contamination. A few (relatively shallow) wells
produced samples with high chloride concentrations;
however, there was no significant association between
chloride concentration and well depth across the study
area. Continued monitoring of locations experiencing
elevated nitrate and chloride concentrations within the
Nitrate observations in this study are well within
the range reported in other parts of the world. For
example, Kolpin et al. (1994) reported nitrate
concentrations above 45 mg/L in six percent of 303
wells tapping shallow aquifers (less than 15 m deep) in
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Hudak, P. F.
study area would help identify contaminant sources,
assess impacts to groundwater, and facilitate
appropriate source control measures.
Nolan, B. T., Ruddy, B. C., Hitt, K. J. and Helsel, D. R.
(1997). Risk of nitrate in groundwaters of the United States
– A national perspective. Environmental Science and
Technology, 31, 2229-2236.
Peckham, R. C., Souders, V. L., Dillard, J. W. and Baker, B.
B. (1963). Reconnaissance investigation of the ground-water
resources of the Trinity River Basin, Texas. Texas Water
Commission, Austin, Texas.
REFERENCES
Baker, B., Duffin, G., Flores, R. and Lynch, T. (1990).
Evaluation of water resources in part of north-central Texas.
Texas Water Development Board, Austin, Texas.
Power, J. F. (1987). The role of legumes in conservation
tillage systems. Soil Conservation Society of America,
Ankeny, Iowa.
Belkhiri, L., Boudoukha, A. and Mouni, L. (2011). A
multivariate Statistical Analysis of Groundwater Chemistry
Data, Int. J. Environ. Res., 5 (2), 537-544.
Puckett, L. J. (1994). Nonpoint and point sources of nitrogen
in major watersheds of the United States. United States
Geological Survey Water Resources Investigation Report,
94-4001, 1-9.
Bouwer, H. (1978). Groundwater hydrology. McGraw-Hill,
New York.
De Roos, A. J., Ward, M. H., Lynch, C. F. and Cantor, K. P.
(2003). Nitrate in public water supplies and risk of colon
and rectum cancers. Epidemiology, 14(6),640-649.
Romanelli, A., Massone, H. E. and Qutrozl, O. M. (2011).
Integrated Hydrogeological Study of Surface & Ground Water
Resources in the Southeastern Buenos Aires Province,
Argentina. Int. J. Environ. Res., 5 (4), 1053-1064.
Eneke, G. T., Ayonghe, S. N., Chandrasekharam, D.,
Ntchancho, R., Ako, A. A.,Mouncherou, O. F. and
Thambidurai, P. (2011). Controls on groundwater chemistry
in a highly urbanised coastal area. Int. J. Environ. Res., 5
(2), 475-490.
Spalding, R. F. and Exner, M. E. (1993). Occurrence of nitrate
in groundwater: A review. Journal of Environmental Quality,
22, 392-402.
EPA, (2009) United States Environmental Protection Agency,
National primary drinking water regulations. United States
Environmental Protection Agency, Washington, D.C.
Strebel, O., Duynisveld, W. H. M. and Bottcher, J. (1989).
Nitrate pollution of groundwater in western Europe.
Agriculture, Ecosystems and Environment, 26, 189-214.
Fried, J. J. (1991). Nitrates and their control in the EEC
aquatic environment. p. 3-11. In I. Bogardi and R. D. Kuzelka
(eds.) Nitrate contamination: Exposure, consequence, and
control. NATO ASI Serial G: Ecological Sciences 309.
Springer-Verlag, Berlin.
TDA, (1985). Texas Department of Agriculture, Agricultural
land and water contamination. Office of Natural Resources,
Austin, Texas.
TWC, (1989). Texas Water Commission, Ground-water
quality of Texas. Texas Water Commission, Austin, Texas.
Hem, J. D. (1985). Study and interpretation of the chemical
characteristics of natural water. United States Geological
Survey Water-Supply Paper, 2254, 1-263.
TWDB, (2003). Texas Water Development Board, A field
manual for groundwater sampling. Texas Water Development
Board, Austin, Texas.
Hudak, P. F. (2000). Regional trends in nitrate content of
Texas groundwater. Journal of Hydrology, 228, 37-47.
Ulery, R. L. and Brown, M. F. (1995). Water-quality
assessment of the Trinity River Basin, Texas: Review and
analysis of available pesticide information, 1968-91. United
States Geological Survey, Austin, Texas.
Hudak, P. F. (2003). Oil production and groundwater quality
in the Edwards-Trinity Plateau Aquifer, Texas, USA. The
Scientific World Journal, 3, 1147-1153.
Ward, M. H., Mark, S. D., Cantor, K. P., Weisenburger, D.
D., Correa-Villasenor, A. and Zahm, S. H. (1996). Drinking
water nitrate and the risk of non-Hodgkins lymphoma.
Epidemiology, 7 (5), 465-471.
Hudak, P. F. (2011). Spatial Distribution of Solutes in Aquifer
Outcrop Zones along the Brazos River, East-Central Texas.
Int. J. Environ. Res., 5 (3), 595-602.
Knobeloch, L., Salna, B., Hogan, A., Postle, J. and Anderson,
H. (2000). Blue babies and nitrate-contaminated well water.
Environmental Health Perspectives, 108 (7), 675-678.
Wilhelm, S. R., Schiff, S. L. and Robertson, W. D. (1996).
Biogeochemical evolution of domestic waste water in septic
systems: 2. Application of conceptual model in sandy
aquifers. Ground Water, 34, 853–864.
Kolpin, D. W., Burkart, M. R. and Thurman, E. M. (1994).
Herbicides and nitrates in near-surface aquifers in the
Midcontinental United States, 1991. United States
Geological Survey Water-Supply Paper, 2413, 1-34.
Zhang, W. L., Tian, Z. X. and Li, X. Q. (1996). Nitrate
pollution of groundwater in northern China. Agriculture,
Ecosystems & Environment, 59 (3), 223-231.
Martínez-Paz, J. M., and Perni, A . (2011). Environmental
Cost of Groundwater: A contingent Valuation Approach,
Int. J. Environ. Res., 5 (3), 603-612.
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